Manufacture of condensation products from aliphatic organic compounds



Patented Sept. 7, 1937 PATENT OFFICE MANUFACTURE OF CONDENSATION PROD- UGTS FROM ALIPHATIG ORGANIC COMP POUNDS om Fuchs, Frankfort-on-the -Main, and wuhcim Querfnrth, Mainz-Mombach, Germany No Drawing. Application March 27, 1934, Serial 717,580. In Great Britain October 26, 1931 lzclaims. (CL-2'60--'138) .This application is a continuation in part of application Serial No. 639,734 filed October. 26,

The present invention relates to the manufa'cture of valuable condensation products from\ 1 the oxygenated derivatives of the paraflln series of hydrocarbons and specifically relates to'the production of alcohols, esters and other valuable derivatives of higher molecular weight from alcohols which contain more than four carbon atoms in the molecule and mixtures of such alcohols with other alcohols by catalytic treatment in the presence of hydrogen.

In carrying out the manufacture according to the present invention we use catalysts'which consist of a diilicultly reducible oxide or mixture of oxides having only feeble or no basic action and being stable at the prevailing temperature, to-

1 gether with a metal or mixture of metals known oxide. The catalyst may be used on suchas pumice or other inert material.

' According to the present invention it is essento have. a hydrogenating or dehydrogenating action and not exceeding in quantity ten percent by weight of complete catalyst. The metal or metals maybe taken in their metallic, state and be admixed as such or the oxide or oxides may be used, it being understood that owing to the use of hydrogen as'hereinbefore mentioned and as hereinafter described the oxide or oxides. will rapidly be reduced. We. may also use, as anaddition in the catalyst, oxides having a basic reaction, but we prefer to limit the amount of these basic oxides so that-the proportion present is always less than the proportion of the other catalytic constituents. We have .found, however, thatit'may be preferable 'to employ a catalyst containing larger amounts of the basic carriers,-

tial that hydrogen or nitrogen should be added to the reaction mixture as it has been found that improved technical results are obtained by this addition; and, moreover, theaddition of hydrogen increases the activity and the life of the catalyst. Suitable amounts of hydrogen arefrom. onehalf mol. hydrogen to three or more mols hydrogen for each mol. of aliphatic compound.

The conversion can be carried out'at temperatures between'150 and 450 C. and atmospheric or increased pressure maybe used. Generally we prefer to use moderately increased pressures up to fifty atmospheres.

'As examples of the metallic oxides of feeble basic action which can be used may be mentioned alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide and so forth, and as titles of higher esters and hi catalytic metals can be mentioned copper, nickel, silver, chromium,'cadmium, zinc, tin, manganese and cobalt. Suitable oxides having a basic reaction are calcium oxide, barium oxide, strontium oxide, magnesia and lithia. By the passage ot a mixture of acetaldehyde and hydrogen, for instance, over a catalyst consisting of alumina and copper, there may be obtained considerable quaner alcohols, and substantially the whole of th acetaldehyde unconverted into the aforesaid higher products is recovered without decomposition.

We have also found that by altering the proportions ofnietal oxide and catalytic metal in the catalyst, thecourse ofthe reaction canbe influenced so that either higher yields of alcohols and the like canbe'produced, or the conversion can be directed towards the production of larger proportions of esters and so forth. It is essential, however, that the proportion of catalytic metal should not exceed ten per centby weight of thetotal catalyst. p D

After the catalytic co'nversionthe products of the reaction may be condensed "and separated, or partially condensed and recirculated over the catalyst. The unconverted starting material maybe recirculated over the catalyst alone or together with any of the products ofthe reaction. The present invention contemplates the preparationiof valuable roducts by passing a mixture of alcohols which ntain more than four carbon atoms in the molecule together with other alcohols over catalysts of the above mentioned type in the presence of hydrogen at temperatures-between and 450"v C. and in some cases at ele- 35 vated pressure. Alcohols having more than four carbon atoms in the molecule may be treated sepa'rately but preferably will 'be treated in mixtures of. which the following are examples. Amy] alcohols, together with methyl, ethyl, butyl, hexyl, heptyl, octyl alcohols, etc. Hexyl alcohols in mixtures'with methyl,- ethyl, butyl, heptyl, octyl alcohols, etc. The mixtures'can be composed 0 in accordance with the law of mass action. Condensations between likemolecules will be more 101- less in the foreground, depending upon the concentration of the molecules involved. Or, in other words, in accordance with the law of mass action.

The following general examples are illustrative I of the invention, but they are in no case to be regarded in a limltative light but merely for purposes of illustration.

Example I The catalyst used is composed as follows:

Grams Magnesia 438 Copper oxide- 19 Alumina hydroxide gel (15 per cent) 264 Iron nitrate 11 Saw dust (700 mesh per sq. cm.) 27 Phosphorous acid 222 M01. per cent. Acetaldehyde (relating to the total amount of carbon in the starting mixture) 1.6

Ethyl alcohol 23 Valerie aldehyde Butyl alcohol 1.1 Amyl alcohol 50.9 'Heptyl alcohol and higher homologues thereof 18.0

' Example I! The mixture indicated in Example I is revised so as to be rich in ethyl alcohol. The resultant products will then contain increased amounts of butyl alcohol.

Example III The mixture in Example I is revised so as to contain an excess of amyl alcohol. The result-' ant product 'will favor the formation of decyl alcohol.

The results set forth in the above three ex?- amples are similar when amyl alcohol and butyl alcohol are passed over a catalyst. If the quantity of butyl alcohol is in excess the reaction product will be rich inoctyl alcohol.

The reaction set forth above may be carried out in the vapor ph or in" the liquid phase in the presence of diluents. The reactions can also be carried out at atmospheric or at elevated pressure.

Example IV The'catalyst employed was composed as follows: Magnesium oxide- (parts Mg by weight) 89 Alumina (parts Al by weight) 8 Copper oxide (parts Cu by weight) 3 As will be observed the amount of basic oxide is considerable. This is because we are here treating a mixture of alcohols including a higher alcohol as hereinbefore mentioned. Actually the mixture consisted of methyl alcohol, butyl alcotion to unchanged components and small,

amounts of acetaldehyde, butyraldehyde and esters of formic acid) were as follows:-

Parts by weight Amyl alcohol 1078 Hexyl alcohol 82 Alcohols of higher boiling point especially heptyl alcohol 480 This example shows that by using a mixture of alcohols including a higher alcohol together with methyl alcohol, the higher alcohols with a boiling point of over C. can be obtained in considerable quantities. It is, for example, possible to take the mixed products resulting from any initial conversion of a'loweralcohol into a higher alcohol and'retreat it according to the present invention for the further conversion into higher alcohols. Similarly it is possible to take the mixed product of any initial conversion of a lower alcohol into a higher alcohol or to take either component of such a product and to mixit with a fresh quantity of an alcohol and subject that mixture to treatment according to the present invention. 1

We claim:--

1. The process of producing valuable condensation products from alcohols having more than four carbon atoms comprising subjecting such alcohols in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide in admixture with a substance taken from a group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, mananese and cobalt and the oxides thereof, said substance not exceeding in quantity 10% by weight of the complete catalyst and in admixture with an alkali earth metal oxide as the preponderant constituent and the reaction temperature ranging from about C. to about 450 C.

2. The process of producing valuable conden- ,sation productsfrom a mixture of amyl alcohol with a normally liquid homologous alcohol coinprising subjecting such mixture in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide in admixture with a substance taken from a group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substance not exceeding in quantity 10% by weight of the complete catalyst and in admixture with an alkali earth metal oxide as the preponderant constituent and the reaction temperature ranging from about 150 C. to about 450 C.

3. The process of producing valuable condensation products from a mixture of hexyl alcohol witha normally liquid homologous alcohol comprising subjecting such mixture in conjunction with hydrogen'to the action of a mixed catalyst comprising essentially a compound taken from a griiup consisting of alumina, uranium oxide, thoria, beryllium. oxide and zirconium oxide in admixture with a substance taken from a group consisting of copper, nickel, silver, chromium, cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substance not exceeding in quantity 10% by weight of the complete cata lyst and in admixture with an alkali earth metal oxide as the pre'ponderant constituent and the reaction temperature ranging from about 150 C. to about 450 C.

4. The process of producing valuable condensation products from alcohols having more than iour carbon atoms comprising subjecting such alcohols in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a compound taken from a group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide in admixture with a substance taken from a group consisting 01' copper, nickel, silver, chromium, cadmium, zinc, tin, manwith magnesia as the preponderant constituent and the reaction temperature ranging from about 150 C. to about 450 C.

5. The process of producing valuable condensation products from a mixture of amyl alcohol with a normally liquidhomologous alcohol comprising subjecting such mixture in conjunction with hydrogen to the action of a mixedcatalyst comprising essentially a compound taken from a.

group consisting of alumina, uranium oxide, thoria, beryllium oxide and zirconium oxide in admixture. with a substance taken from a groupconsisting of copper, nickel, silver, chromium, I

cadmium, zinc, tin, manganese and cobalt and the oxides thereof, said substance not exceeding in quantity 10% by weight of the-complete catalyst and in admixture with barium oxide as the preponderant constituent and the reaction temperature ranging from about150 C. to about 450 C. Y

6. The process of producing valuable condensation products from a mixture of amylalcohol.

with a normally liquid homologous alcohol comprising subjecting such mixture in conjunction with hydrogen to'the action of a mixed catalyst comprising essentially a compound taken from a group consisting of alumina, uranium oxide,

thoria, beryllium oxide and zirconium oxide in admixture with a substance taken from a group consisting of copper, nickel, silver, chromium,

cadmium, zinc, tin, manganese and cobalt andv the oxides thereof, said substance not exceeding in quantity 10% by weight of the complete catalyst and in admixture with calcium oxide as tion products from an alcohol having more than four-carbon atoms comprising subjecting such alcohol in conjunctinn with hydrogen to the action ot'a mixed catalyst comprising essentially a dehydrating metal oxide which will be stable in the reaction in admixture with a hydrogenating 'metal not exceeding in quantity 10% by weight I of the complete catalyst and an allsali earth metal oxide as the. preponderant constituent, the reac- 3 tion temperature ranging i'rom about 1501c. to about 450' C. i I

8. The process of producing valuable conden-,

sationproducts from alcohols having more than four carbon atoms comprising subjecting such alcohols in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a dehydrating metal oxide which will be stable in the reaction in admixture with a hydrogenating metal oxide not exceeding in quantity 10% by weight of the complete catalyst and an alkali earth metal oxide as the preponderant constituent, the reaction temperature ranging from about C. to about 450 C. v

9. The process otproducing valuable condensation products from alcohols having more than four carbon atoms comprising subjecting such alcohols in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a dehydrating metal oxide which will be stable in the reaction with a hydrogenating metal not exceeding in quantity 10% by weight of the complete catalyst and with magnesia as the preponderant constituent, the reaction temperature ranging from about 150 C. to about 450 C.

10. The process of producing valuable condensation products from alcohols having more than four carbon atoms comprising subjecting such alcohols in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a dehydrating'metal' oxide which will be stable in the reaction with a hydrogenating metal oxide not exceeding in quantity 10% by weight ofthe complete catalyst and with magnesia as the preponderant constituent, the reaction temperature ranging from about 150 C. to about 450 C.

11. The process of producing valuable condensation products from alcohols having more thantour carbon atoms comprising subjecting such alcohols in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a dehydrating metal oxide which will be stable in the reaction with'a hydrogenating metal not exceeding in quantity 10% by weight oi! the com- ,plete catalyst and with barium oxide as the preponderant constituent the reaction temperature ranging from about 150 C. to about 450 C.

12. The process 0! producing valuable condensation products from alcohols having more thanhtour carbon atoms comprising subjecting such alcohols in conjunction with hydrogen to the action of a mixed catalyst comprising essentially a dehydrating metal oxide which-will be stable in the reaction with a hydrogenating metal not exceeding in quantity 10% by weight 01' the complete catalyst and with calcium oxide as the preponderant constituent, the reaction temperature ranging from about 150 C. to about450 C.

o'rro FUCHS. wmnnur QUERFUR'I'H. 

